First Synthesis of Aliphatic Nitro‐<i>NNO</i>‐azoxy Compounds

Abstract

The first aliphatic nitro‐ NNO ‐azoxy compounds were synthesized by substitutive nitration of appropriate tert ‐butyl‐ NNO ‐azoxy compounds with nitronium tetrafluoroborate. Nitro(nitro‐ NNO ‐azoxy)methane ( 1 ), ( tert ‐butyl‐ NNO ‐azoxy)(nitro‐ NNO ‐azoxy)methane ( 2 ), bis(nitro‐ NNO ‐azoxy)methane ( 3 ), and 2‐nitro‐2‐(nitro‐ NNO ‐azoxy)propane ( 4 ) were prepared. Compound 4 with the nitro‐ NNO ‐azoxy group bound with the tertiary C atom appeared most stable (DSC, onset temperature of decomposition 104 °C). Compound 2 was less stable (DSC, onset temperature 88 °C). Compounds with strong electron withdrawing substituents had the least stability, assumingly, due to rather high acidity of CH protons alongside with instability of C ‐anions of nitro‐ NNO ‐azoxy compounds.